Separation and purification of green or water-soluble sulphonic acids



Patented Jan. 30, 1945 SEPARATION AND PURIFICATION OF GREEN BWATER-SOLUBLE SULPHONIC ACIDS Oliver H. P. Dawson,

Baytown, Ten, assignor to Standard Oil Development Company, acorporation of Delaware No Drawing. Application November 25, 1943.Serial No. 511,738

10 Claims.

The present invention is directed to the production of purifiedsulphonic acids and salts thereof from petroleum.

The treatment of petroleum oils with sulphuric mixture in an amountnecessary to precipitate most of the objectionable coloring matter, butnot the sulphonic acids. The sulphonic acids remaining in solution inthe toluene-hexane mixture are washed out with water, neutralized andacid serves to remove asphaltic materials and, to a greater or lesserdegree, aromatics, unsatudried. rates and other undesirable components.This To illustrate the application of my invention treatment results inthe formation of an acid the following example is given. 3 liters of 75sludge which, in the past, has been chiefly of phenol extract 1 wastreated at 90 F. with ten interest in that its disposal offered aconsiderable successive treats with 40 pounds'of 98% sulphuric refineryproblem. acid per barrel of oil. The sludge obtained from This acidsludge contains sulphonation prodeach successive lO-pound acidapplication was ucts which can be recoveredby extraction. The mixed with1.4 times its volume of toluene. a alkali salts or these sulphonic acidsare waterport n f th slud e in int soluti n with soluble and possesswetting or detergent properthe toluene. Sulphuric acid of about 1.7specific ties. It is generall known that the first acid gravi y. whi h ws ins l bl as parated from application removes asphaltic materials andpolythe toluene solution. The toluene-sludge solurnerizes oleflns, andthat successive clumps of tion was mixed with a volume of hexane equalacid cause sulphonation to predominate. In to twice that of the toluenepreviously used, white oil production and other refinery processes,whereupon considerable coloring matter and he r w r su essive acid dumpsare apother impurities were precipitated. The sulp i sulph ion in sewith each acid nphonic acids remaining in solution in the toluenep n-The pa a and P fi of hexane mixture were extracted with water. neuthesesulphonation products, however, is contmlized with causticand Sidered tobe quite difllcull- The following tabulated data further illustrate Theseparation and purification of sulphonlc the extraction and purificationoperation: acids (especially those produced in white oil pro- Todetermine the effect of the acid treating duction) can be easilyaccomplished by taking temperature on the yield of water-solublesuladvantage of their solubility in aromatic comphonic acids, a 3-litertreat similar to the one desludgelrom'lroat No.

1 2 a 4 s e 1 a o 10 S ee cc.. 345 3:5 231 282 247 245 200 260 243 m0Tolueneadded ,.cc 493 457 422 415 876 381 390 370 355 336 Sulphuric acidseparated. 75 115 142 142 I48 141 127 149 125 123 s iflosravltyat90F--1.5a 1.7l 1.14 1.73 1.13 1.12 1.11 1.13 1.13 1.13Budgesolublelntoluene... mi] 41.5 65.0 78.0 74.0 60.0 34.0 99.0 110.087.0 Herons added e sou am 752 734 730 no no 062 lmpuritiegfmcipitatedon -1.@ 16.0 27.0 20.0 25.0 13.0 10.0 30.0 46.0 no.0 pho losoaa 12.025.5 33.0 52.0 49.0 42.0 24.0 64.0 64.0 57.0

Purified sulpbonic soap, total gma, 427.5.

Purified sulphcnic soap. rcent by Pounds dry soap per 1,008

I When and water-solo le.

is poured into the toluene-sludge we! ht on oil charge, 14.5. bbls. oilcharg e, 50,000. to a powder and passed through e 404116811 screen thepowder had a cream color, and was entirely scribed above was made at atemperature of 125 F. The aromatic solvent used in this case was a plantxylol out having an I. B. P. of 274 F. and a F. B. P. oi 320 F. Theparalfin precipitant used was a parafiinic railinate obtained by S0: ex-

Phenol extract or a naphthenic base lube oil having a Saybolt vino-ll;at 100' ii. of about locondl.

traction of hydroformed naphtha having an I. B. P. of 218 F. and a F. B.P. of 410 F. (95% at 272 F.). "*e data obtained are as follows:

are cream color, whereas those produced by the prior methods mentionedabove have the color of ordinary building sand. The sulphonates pro-Sludge from Treat No.

1 2 a 4 a c 1 s Sludge .00.. 350 355 350 257 270 255 250 165 21GAromatic added i- Cl: 450 400 491 374 280 302 are 340 258 302 Sulphuricacid separated .120 i 100 185 100 134 100 105 121 108 112 108 Specificgravity 00" r 1.10 1.12 1.12 1.73 1.73 1.71 1.12 1.71 1.14 1.14Raflluato added 0C 900 no 050 748 760 124 753 can 516 004 Purified soapgms 38 27 49 (i2 70 74 B9 41 75 Purified soap, total gins, 545. Purifiedsoap, percent by weight on oil charge 18.4. Pounds dry soap per 1,000bills. oil charge, 03300.

The plant application of my invention involves duced by the method ofthe present invention are the following operations: acceptable to thehigh grade soap trade, while The sludge obtained, as in the treatinoperathose produced by the prior methods referred to tlon describedabove, is intimately mixed, withabove are not. out heating, with fromone to 1 volumes of an While several examples of aromatic solventsaromatic solvent (toluene, xylene or any naphtha useful for the initialextraction step have been of 75% or greater aromatic content), andsettled mentioned, it is to be understood that no attempt for severalhours The sulphuric acid of about has been made to give an exhaustivelist. In 1.? specific gravity is then drawn oil from the gene y so tWhichis predominantly bottom. The insoluble sludge portion is next maticin character can be used. In like manner, transferred to another kettleto be processed for the paraflinic solvent need not be selected fromfuel. the specific examples given. Many paraffinic sol- In order toprecipitate coloring matter and vents, such as petroleum ether, octaneand others, other impurities from the aromatic soluble sludge readilysuggest themselves. It is required only portion left, a paraflinicnaphtha (hexane or a that this solvent be predominantly paraflinic. Itlow-boiling raflinate) is add i an amount is preferred, as previouslyindicated, that the two ranging from equal to twice that of the aromaticypes of solvents be of distinctly different boiling previously added,The impurities precipitated points to facilitate separation thereof forre-use. from solution are dark colored sulphonic acids It ay bementioned t t @0101 Of h P o ct which may be used for purposes wherepurity is appears to improve as the ratio of parafinic to not required.aromatic solvent increases. It is a fact, however, Thearomatic-parafllnic-sludge solution is that some color improvement isachieved even pumped to a clean agitator where the sulphonic h n e Pa cvent is used in lesser acids are extracted with water, neutralized with40 mounts than the aromatic solvent. sodium hydroxides, and dried. Thedried soa In the practice of the present invention it is may be groundto a powder if required or handled p t t at t u n of steps described ilumps, above be observed, since very little, it any, of Thearomatic-parafiinic mix is then fractionthe sludge sulphonlc acidsdissolve in paramnlc ated for further use. To facilitate separation or sv nts. r t an appr iable extent in mixtures the two naphthas, the finalboiling point of one of paraflinic and aromatic solvents in which theshould be slightly lower than the initial boiling parafllnic solvent prmin tes. In one operapoint of the other. tlon an acid sludge containingsulphonic acid Y1 1d of soap vary nd depend upon th st k bodies wascontacted with a parafllnic naphtha treated and upon the acid treatingtemperature. fraction- The Paramnic p t mction re- Yields obtainablewhen treating '75 phenol extract mined Substantially 6010116555 and Onpp with ten LO-pound dumps of 98% sulphuric acid tlon of water theretoit was found that little, it are as follows: any, otfhthe1 sllphon li lcacidsamhad been extracted rom e s u go. e par nic naphtha fracggfsg ;3'666 90-100 125 tlon seems to act as an anti-solvent on the aroextract 500 63 80 matic extract selectively rejecting color bodies from theextract solution. The reason for this Other methods for recoveringsulphonic acids selective rejection or the color bodies is not unfromthese acid sludges have hitherto been proderstood, but it is believedthat ther are d posed. Among these are extraction of the sludge 0colored impurities present in the acid sludge with amyl alcohol followedby washing of the exwhich are less soluble in the aromatic solvent tractwith water and recovery of the sulphonic than in the dilute acid. Thesedark colored acids in neutralized form. from the water soluimpuritiesare taken up in part from the dilute tion, and extraction of the acidsludge with aroacid by the aromatic solvent but are precipitated maticnaphtha iollowedbywashinc 01' the extract 65 on addition of theanti-solvent or parafilnic with water and recovery of the sulphonicacids in naphtha in which the dark colored material and neutralized formfrom the water extracts. Both sulphonic acids are substantiallyinsoluble. Of these meth Produce Bulpbonates ch are Thus, unless thesequence of steps of the present many shades darker than those obtainedby the invention is followed, little, it any, segregation method of thepresent invention. An interesting or the sulphonic acids, to say nothingof purificafact is that the sulphonic acids produced by these tlon,occurs. methods have substantially the same color as the In the appendedclaims sulphonic acids and impure constituents precipitated by theparaflinlc soaps thereof are embraced in the term sulsolvent in themethod of the present invention. phonic acid bodies." The urifiedsulphonates of the present invention The nature and objects of thepresent invention having been fully described, what I wlsh to claim asnew and useful and to secure 1: Letters Patent is:

1. In a method for producing sulphonic acid bodies from the acid sludgeobtained in the treatment of petroleum oils with concentrated sulphuricacid, the steps which comprise extracting the acid sludge with apredominantly aromatic hydrocarbon solvent, isolating the extract,mixing the extract with a predominantly paraflinic hydrocarbon solventto precipitate colored impurities, separating the precipitatedimpurities from the solvent mixture and recovering a sulphonic acid bodyfrom the latter.

2. In a method for producing sulphonic acid bodies from the acid sludgeobtained in the treatment of petroleum oils with concentrated sulphuricacid for the production of white oil, the steps which compriseextracting the acid sludge with a predominantly aromatic hydrocarbonsolvent, isolating the extract, mixing the extract with a predominantlyparafllnic hydrocarbon solvent to precipitate colored impurities,separating the colored impurities from the solvent mixtures andrecovering a sulphonic acid body from the latter.

3. A method according to claim 1 in which the predominantly paraffinicsolvent is used in an amount at least equal to that of the predominantly aromatic solvent.

4. A method for producing sulphonic acid bodies from petroleum oil whichcomprises treating petroleum oil with concentrated sulphuric acid at atemperature in excess of 1000 F. to

produce an acid sludge, the acid sludge with a predominantly aromatlchydro- 1 carbon solvent, isolating the extract, mixing the extract witha predominantly paraflinic hydrocarbon solvent to precipitate coloredimpurities, separating the colored impurities from the solvent mixtureand recovering a sulphonic acid body from the latter.

5. A method according to claim 4 in which the petroleum oil is oneadapted to yield white oil upon treatment with concentrated sulphuricacid.

6. A method according to claim 4 in which the predominantly paraflinicsolvent is employed in an amount at least equal to that 01' thepredominantly aromatic solvent.

7. A method according to claim 4 in which the aromatic solvent istoluene and the parailinic solvent is hexane.

8. A method according to claim 1 in which the aromatic solvent istoluene and the paraflinic solvent is hexane.

9. A method according to claim 1 in which the predominantly aromaticsolvent and the predominantly parafiinic solvent have suflicientlydin'erent boiling points to permit easy separation of the two bydistillation.

10. A method according to claim 4 in which the predominantly aromaticsolvent and the predominantly paraflinic solvent have suiiicientlydifierent boiling points to permit easy separation of the two bydistillation.

OLIVER H. P. DAWSON.

CERTIFICATE OF CORRECTION Patent No. 2,568, 52.

OLIVER H. P. DAWSON.

January 50, 1915.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 5,first column, line al claim l for "10oo F."

read -100 F.--; and that the said Letters Patent should be read withthis correction therein that the same may conform to the record of thecase in the Patent Office.

Signed and sealed this 15th day of Hay, .A. D. 1915.

(Seal Leslie Frazer Acting Commissioner of Patents.

tion having been fully described, what I wlsh to claim as new and usefuland to secure 1: Letters Patent is:

1. In a method for producing sulphonic acid bodies from the acid sludgeobtained in the treatment of petroleum oils with concentrated sulphuricacid, the steps which comprise extracting the acid sludge with apredominantly aromatic hydrocarbon solvent, isolating the extract,mixing the extract with a predominantly paraflinic hydrocarbon solventto precipitate colored impurities, separating the precipitatedimpurities from the solvent mixture and recovering a sulphonic acid bodyfrom the latter.

2. In a method for producing sulphonic acid bodies from the acid sludgeobtained in the treatment of petroleum oils with concentrated sulphuricacid for the production of white oil, the steps which compriseextracting the acid sludge with a predominantly aromatic hydrocarbonsolvent, isolating the extract, mixing the extract with a predominantlyparafllnic hydrocarbon solvent to precipitate colored impurities,separating the colored impurities from the solvent mixtures andrecovering a sulphonic acid body from the latter.

3. A method according to claim 1 in which the predominantly paraffinicsolvent is used in an amount at least equal to that of the predominantly aromatic solvent.

4. A method for producing sulphonic acid bodies from petroleum oil whichcomprises treating petroleum oil with concentrated sulphuric acid at atemperature in excess of 1000 F. to

produce an acid sludge, extracting the acid sludge with a predominantlyaromatlc hydro- 1 carbon solvent, isolating the extract, mixing theextract with a predominantly paraflinic hydrocarbon solvent toprecipitate colored impurities, separating the colored impurities fromthe solvent mixture and recovering a sulphonic acid body from thelatter.

5. A method according to claim 4 in which the petroleum oil is oneadapted to yield white oil upon treatment with concentrated sulphuricacid.

6. A method according to claim 4 in which the predominantly paraflinicsolvent is employed in an amount at least equal to that 01' thepredominantly aromatic solvent.

7. A method according to claim 4 in which the aromatic solvent istoluene and the parailinic solvent is hexane.

8. A method according to claim 1 in which the aromatic solvent istoluene and the paraflinic solvent is hexane.

9. A method according to claim 1 in which the predominantly aromaticsolvent and the predominantly parafiinic solvent have suflicientlydin'erent boiling points to permit easy separation of the two bydistillation.

10. A method according to claim 4 in which the predominantly aromaticsolvent and the predominantly paraflinio solvent have suiiicientlydifierent boiling points to permit easy separation of the two bydistillation.

OLIVER H. P. DAWSON.

CERTIFICATE OF CORRECTION Patent No. 2,568, 52.

OLIVER H. P. DAWSON.

January 50, 1915.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 5,first column, line al claim l for "10oo F."

read -100 F.--; and that the said Letters Patent should be read withthis correction therein that the same may conform to the record of thecase in the Patent Office.

Signed and sealed this 15th day of Hay, .A. D. 1915.

(Seal Leslie Frazer Acting Commissioner of Patents.

